Bifunctional reactive dyestuffs containing the 2-(N-substituted amino)-4-(N-phenylamino)-1,3,5-trlazinyl moiety

ABSTRACT

Improved reactive dyestuffs have the following formula ##STR1## in which the substituents have the meaning given in the description.

The present invention relates to new reactive dyestuffs of the formula##STR2## in which D denotes a radical of an organic dyestuff,

W denotes a direct bond or bridging member,

R₁ denotes H or alkyl,

R₂ denotes H or alkyl,

R denotes H, C₁ -C₂ -alkyl, halogen, C₁ -C₄ -alkoxy,

B denotes C₂ -C₆ -alkylene, which, if desired, is branched and/orinterrupted by hetero atoms or groups containing hetero atoms,

X denotes F, Cl, ##STR3## Z denotes --CH═CH₂, --CH₂ --CH₂ --OSO₃ H,--CH₂ --CH₂ --Cl, --CH₂ --CH₂ --Br, --CH₂ --CH₂ --S₂ O₃ H, --CH₂ --CH₂--O--CO--CH₃, --CH₂ --CH₂ --OPO₃ H₂, --CH₂ --CH₂ --OH,

n denotes 1 or 2.

Examples of radicals D are those from the monoazo, polyazo, metalcomplex, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine,phenazine, stilbene, triphenylmethane, xanthene, thioxanthone ornitroaryl series. A particularly suitable radical of an organic dyestuffis one containing one or more water-solubilising groups, in particularsulpho groups.

For the alkyl, aryl, aralkyl, hetaryl, alkoxy, halogen and acylaminoradicals mentioned in the present application and for the bridgingmembers the following applies:

Alkyl groups are understood to mean in particular those having 1 to 4 Catoms, with or without the substituents, for example halogen, such as Clor Br, OH, CN or OSO₃ H.

Aryl groups are understood to mean in particular phenyl radicals, withor without substituents, for example halogen, such as Cl and Br, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylsulphonyl, NO₂, CN, CF₃, SO₃ H,COOH.

Aralkyl radicals are understood to mean in particular benzyl radicals,with or without the substituents mentioned for the phenyl radicals.

Alkoxy radicals are understood to mean in particular those having 1 to 4C atoms.

Halogen is understood to mean in particular chlorine or fluorine.

Acylamino radicals are understood to mean in particular those having 1to 4 C atoms, such as formylamino, acetylamino, propionylamino orn-butyrylamino.

Examples of suitable bridging members W are: ##STR4## in which R₁represents hydrogen or alkyl, and alkylene denotes an alkylene radicalhaving 1 to 6 C atoms.

Alkylene radicals are --CH₂ --, ##STR5## --(CH₂)₃ --, --(CH₂)₄ --,--(CH₂)₆ --.

Examples of suitable aliphatic bridging members B are ##STR6##

The present invention furthermore relates to the preparation of thereactive dyestuffs of the formula (I) by methods known per se:

a) either by condensation of dyestuffs of the formula ##STR7## in whichD, W, R₁ and n have the abovementioned meaning, ps with n mol oftrihalogenotriazines of the formula ##STR8## in which X' is F, Cl togive compounds of the formula ##STR9## and further condensation of thecompounds of the formula (IV) with n mol of the components of theformula ##STR10## in which R₂, R, B and Z have the abovementionedmeaning, or

b) in reverse order, by condensation of trihalogenotriazines of theformula (III) with the components of the formula (V) to give the primarycondensation products ##STR11## in which X', R₂, R, B and Z have theabovementioned meaning, and further condensation with n mol of thecompounds of the formula (VI) with the dyestuffs of the formula (II), or

c) by condensation of suitable precursors with trihalogenotriazines(III) and the components of the formula (V) or by condensation ofsuitable precursors with the primary condensation products of theformula (VI), followed by dyestuff synthesis, and

d) if desired, by exchange of the halogen atom X' for the radical ofpyridine-3-carboxylic acid in the synthesised halogenotriazine dyestuff.

The condensations of the starting components with thetrihalogenotriazines are carried out irrespective of the order inaqueous or organic-aqueous media in the presence of acid-binding agents.Depending on the nature of the starting components, the first step ofthe condensation is carried out in pH ranges of 2 to 8, preferably 3 to7, and at temperatures of 0° to 40° C., preferably 0° to 25° C.

Exchange of the second halogen atom of the triazine is completed in thepH range of 4 to 10, preferably 5 to 9, and in the temperature range of0° to 60° C., preferably 0° to 30° C.

Examples of acid-binding agents are carbonates, hydroxides orphosphates, such as sodium carbonate, sodium bicarbonate, dilute sodiumhydroxide solution, di-or trisodium phosphate or sodium fluoride.

If it is desired for the condensation or the dyestuff synthesis to leaddirectly to a dyestuff solution or to a liquid dyestuff preparation, theuse of lithium carbonates or lithium hydroxide may be advantageous, ifappropriate in combination with solubilising agents and/or stabilisingbuffer systems. Other conversion reactions of the dyestuffs or theirprecursors, such as metallisation reactions, sulphonations orintroduction of acylamino groupings can in general be carried out in anydesired steps of the dyestuff syntheses.

Particularly valuable dyestuffs of this series are water-soluble azo,formazan, anthraquinone, triphendioxazine and phthalocyanine dyestuffs,and in particular those having sulpho and/or carboxyl groups. Thedyestuffs can be either metal-free or metal-containing, their preferredmetal complexes being the copper, nickel, chromium and cobalt complexes.

Suitable dyestuff radicals D or amino-containing dyestuffs underlyingthe dyestuffs of the formula (I) are described in the literature in verylarge numbers. Examples are:

EP-A 54,515, EP-A 69,703, EP-A 70,807, German Auslegeschrift 3,222,726,German Auslegeschrift 2,650,555, German Auslegeschrift 3,023,855, GermanAuslegeschrift 2,847,938, German Auslegeschrift 2,817,780, GB-A2,057,479, German Auslegeschrift 2,916,715, German Auslegeschrift2,814,206, German Auslegeschrift 3,019,936, EP-A 45,488 andVenkataraman: The Chemistry of Synthetic Dyes, Vol. VI, Chapter II, p.211-325, New York, London, 1972.

Examples of important azo dyestuffs are those of thebenzene-azo-naphthalene series, bis(benzeneazo)naphthalene series,benzene-azo-5-pyrazolone series, benzene-azo-benzene series,naphthalene-azo-benzene series, benzene-azo-aminonaphthalene series,naphthalene-azo-naphthalene series, naphthalene-azo-5-pyrazolone series,benzene-azo-pyridone series, benzene-azo-aminopyridine series,naphthalene-azopyridone series, naphthalene-azo-aminopyridine series andof the stilbene-azo-benzene series, in this case too sulpho-containingdyestuffs being preferred. In the case of metal-complex azo dyestuffs,the groups bound in the form of a metal complex are preferably in the opositions relative to the azo group, for example in the form ofo,o'-dihydroxy-, o-hydroxy-o'-carboxy, o-carboxy-o'-amino-ando-hydroxy-o'-amino-azo groupings.

Preferred dyestuffs are those of the formulae (VII) to (XXIII) below, inwhich in general A contains a radical of the formula ##STR12## and X,R₂, R, B and Z have the abovementioned meaning.

Preferred dyestuffs are those of the formulae (VII) to (XXIII) below##STR13## R₃ alkyl, alkoxy, halogen, R₄ H, alkyl, aryl, hetaryl, aralkyl

R_(VII) COOH, CH₃ ##STR14## R₃ alkyl, alkoxy, halogen, R₄ alkyl,aralkyl, aryl,

R₅ alkyl, aryl, aralkyl, hetaryl,

R₆ H, COOR₃, ##STR15## CN, CH₂ --SO₃ H, SO₃ H, ##STR16## R₃ alkyl,alkoxy, halogen

R₇ H, alkyl, alkoxy, acylamino, amino

o,p in o or p position relative to the azo group ##STR17## R₃ alkyl,alkoxy, halogen R₇ alkyl, alkoxy, arylamino

R₈ alkyl, alkoxy, acylamino, ureido

o in ortho position relative to the azo group

R₉ N₈, NO₂

Azo derivatives of this type can be converted to 1:1 (Cu, Ni) or 1:2(Cr, Co) metal complexes (symmetrical and unsymmetrical). ##STR18## R₁₀H, C₁ -C₄ -alkyl, halogen (Cl, Br) C₁ -C₄ -alkoxy, carboxyl, SO₃ H,

R₁₁ H, C₁ -C₄ -alkyl, SO₃ H

R₁₂ H, C₁ -C₄ -alkyl, Cl, Br,

R₁₃ H, C₁ 14 C₄ -alkyl, ##STR19## R₄ H, alkyl, R₁₀ H, SO₃ H, COOH

Pc Cu or Ni phthalocyanine radical ##STR20## R₈ alkyl, halogen,alkylsulphonyl D substituent capable of complex formation, such as, forexample, OH, COOH, ##STR21## R₃ alkyl, alkoxy, halogen K radical of acoupling component, suitable coupling components being in particularthose for the pyridone, pyrazolone, acetoacetylarylide andnaphtholsulphonic acid series. ##STR22## where R₂ alkyl, halogen

R₃ alkyl, alkoxy

K radical of a coupling component ##STR23## R₃ alkyl, alkoxy, arylamino##STR24## R₃ alkyl, alkoxy R₈ H, NH₂, arylamino ##STR25## R₃ alkyl,alkoxy R₈ H, NH₂, arylamino

Compounds of the formula (V) and methods for their preparation aredescribed in European Patent 0,355,492.

The reactive dyestuffs of the formula (I) are suitable for the dyeingand printing of the wide range of substrates, such as silk, leather,wool, synthetic polyamide fibres, but in particular ofcellulose-containing materials of fibrous structure, such as linen,cellulose, regenerated cellulose and in particular cotton. They aresuitable not only for the exhaust method but also for the dyeing by thecustomary pad-dyeing processes, in which the material to be dyed isimpregnated with aqueous and, if desired, also salt-containing dyestuffsolutions, and the dyestuffs are fixed after an alkaline treatment or inthe presence of alkali, if desired with the application of heat.

The reactive dyestuffs of the formula (I) are distinguished by highreactivity and excellent fixation properties. Owing to theirbifunctionality, they give high fixation yields even from a long liquor.They are characterised by a relative independence of the yield from thedyeing temperature and can therefore be used in the exhaust method atlow to medium dyeing temperatures. In the pad-steaming process, theyrequire only short steaming times. They produce dyeings of high colourstrength and good light and wet fastness properties.

EXAMPLE 1

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid asmonosodium salt are dissolved in 800 ml of water at a pH of 6.5. Aftercooling to 0° C., 21.5 ml of cyanuric fluoride are swiftly run in, andthe pH is maintained at 4.0 to 4.5 with 20% strength sodium carbonatesolution and the temperature is further maintained at around 0° C.

78 g of the component of the formula ##STR26## prepared by the proceduregiven in European Patent 0,355,492 are dissolved in 500 ml of water at0° to 3° C. with the addition of 60 ml of 10% strength lithium hydroxidesolution up to a pH of 6.9. Both solutions are combined and the pH inthe reaction mixture is maintained at 5.0 to 5.2 with 2N sodiumcarbonate solution.

51.3 g of 2-aminonaphthalene-1-sulphonic acid are dissolved in 575 ml ofwater by neutralisation with sodium hydroxide solution at a pH of 6.5and 0° C. 57.5 ml of concentrated hydrochloric acid are added in oneportion, and the mixture is then diazotised using 57.5 ml of 4N sodiumnitrite solution. Stirring is continued for one hour, and any excessnitrite is then destroyed with sulphamic acid solution.

The diazo suspension obtained is then stirred into the solution preparedabove at 0° to 5° C., while maintaining the pH in the mixture at 7. 0with 2N sodium carbonate solution. After 3 hours, the temperature isallowed to increase to 20° C. and the mixture is stirred until thecoupling reaction is complete. The dyestuff obtained of the formula##STR27## is salted out with potassium chloride, isolated and, afteraddition of a small amount of phosphate buffer, dried at 50° C. invacuo.

It dyes cotton from a long liquor at an optimum dyeing temperature of50° C. in bluish red hues having high fixation yields.

λ_(max). =545 nm in water.

EXAMPLE 2

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid are reactedas in Example 1 with 21.5 ml of cyanuric fluoride. A solution of 78 g ofthe component ##STR28## obtained by neutralisation in 400 ml of water upto a pH of 6.5 and cooled to 0° to 3° C. is then added over a period ofa few minutes, while maintaining the pH at 5.2 with 2N sodium carbonatesolution.

When condensation is complete, a diazo suspension, prepared according toExample 1 from 51.3 g of 2-amino-naphthalene-1-sulphonic acid, is added.During this, the pH of the coupling mixture is maintained at 7.0 to 7.5with sodium carbonate solution. The temperature is allowed to increasegradually to 10° C. over a period of 21/2 hours and then to 20° C.overnight, while further maintaining the PH at 7.0. The partiallyprecipitated dyestuff is salted out further with sodium chloride,filtered off with suction and washed with 25% strength sodium chloridesolution. After addition of phosphate buffer, it is dried at 50° C. invacuo.

It has the formula ##STR29## and dyes cotton in bluish red hues at anoptimum dyeing temperature of 50° C. and with a high fixation yield.

λ_(max). =545 nm in water.

EXAMPLE 3

41.7 g of the azo compound of the formula ##STR30## are dissolved in 800ml of water by adjusting the pH to 4.5 with 2N sodium hydroxidesolution. After cooling the solution to 0° C., 8.2 ml of cyanuricfluoride are added dropwise over a period of 10 minutes, and the pH ismaintained at 4.5 to 4.7 with 2N sodium carbonate solution. Stirring iscontinued for another 10 minutes, and a neutral solution of 40.5 g ofthe component of the formula ##STR31## in 150 ml of water, obtained fromthe sulpho- and sulphate-free compound by treatment in 20% strengtholeum and work-up by the procedure given in European Patent 0,355,492,is then added. While this compound is metered in, the temperature isfurther maintained at 0° to 2° C. and the pH is maintained at 5.2 to 5.5with sodium carbonate solution. After 2 hours, the temperature isallowed to rise to 20° C. After condensation is complete, the dyestuffis salted out with potassium chloride, filtered off with suction, washedwith 15% strength potassium chloride solution and, after addition of asmall amount of phosphate buffer solution, dried at 50° C. in vacuo.

The dyestuff of the formula ##STR32## dyes cotton from a long liquor atan optimum dyeing temperature of 50° C. and with a high fixation yield,in scarlet hues.

λ_(max). =501 nm in water.

EXAMPLE 4

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid arecondensed, by the procedure of Example 1, with 21.5 ml of cyanuricfluoride. A solution of 41.3 g of the component of the formula ##STR33##in 130 ml of water which is cooled to 0° to 3° C. and adjusted to a PHof 5 is run in over a period of 10 minutes, while maintaining the pH at5.2 with 2N sodium carbonate solution. After 21/2 to 3 hours,condensation is complete.

51.3 g of 2-aminonaphthalene-1-sulphonic acid are diazotised by theprocedure of Example 1, and the diazo suspension is added to the abovecondensation solution in portions. During this, the pH of the reactionmixture is maintained at 6.5. After the addition, the pH is maintainedat 7.0 with dilute sodium carbonate solution and cooling is continued.The temperature is allowed to rise to 20° C. overnight and the dyestuffis then salted out. After buffering, it is dried at 50° C. in vacuo.

The dyestuff of the formula ##STR34## dyes cotton from a long liquor atan optimum dyeing temperature of 40° C. and with a high fixation yieldin bluish red hues.

λ_(max). =545 nm in water.

EXAMPLE 5

In accordance with the procedure of Example 1, a solution of thecoupling component ##STR35## is prepared from 78.4 g of1-amino-8-hydroxynaphthalene-3,6-disulphonic acid, 21.5 ml of cyanuricfluoride and 78 g of 3-(4-aminophenoxy)propyl β-sulphatoethyl sulphone.

39.8 g of 2-aminobenzenesulphonic acid are dissolved in 300 ml of waterand 112 ml of 2N sodium hydroxide solution at a pH of 6. 57.5 ml of 4Nsodium nitrite solution are added. The solution obtained is run into aninitially introduced mixture of 200 ml of water, 60 ml of concentratedhydrochloric acid and 2.5 ml of 4N sodium nitrite solution at 0° to 2°C. over a period of 30 minutes. Stirring is then continued for 1 hour, asmall amount of excess nitrous acid is removed using sulphamic acid, andthe diazo suspension obtained is stirred into the above solution of thecoupling component at 0° to 3° C., while maintaining the pH in theresulting mixture at 6.5 by simultaneous addition of 2N sodium carbonatesolution. After stirring for two hours with cooling, the temperature isallowed to rise to 20° C.

After coupling is complete, the dyestuff is salted out with potassiumchloride, filtered off with suction, washed with 20% strength potassiumchloride solution and, after buffering, dried at 50° C. in vacuo.

It has the formula ##STR36## and dyes cotton from a long liquor at anoptimum dyeing temperature of 50° C. and with good fixation yields inred hues.

λ_(max). =532 nm in water.

EXAMPLE 6

74.8 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid arecondensed by the procedure of Example 1 with 21.5 ml of cyanuricfluoride.

A solution of 84.9 g of ##STR37## in 250 ml of water which is cooled to0° to 3° C. and adjusted to a pH of 5 is run in over a period of 10minutes, while maintaining the pH at 5.2 with 2N sodium carbonatesolution.

The solution is prepared by sulphation of2-[2-(4-aminophenoxyethoxy)ethoxy]-2-hydroxyethyl sulphone in the2.5-fold volume of 96% strength sulphuric acid at 0° to 3° C., stirringthe mixture into ice, neutralising the solution up to a pH of 5 withcalcium carbonate, filtering the calcium sulphate and concentrating thefiltrate.

69.7 g of 2-aminonaphthalene-1,5-disulphonic acid are dissolved in 500ml of water by adding sodium hydroxide solution up to a pH of 7. Thesolution is cooled to 0° C., 67.5 ml of 4N sodium nitrite solution and300 g of ice are added, and 60 ml of concentrated hydrochloric acid areadded in one portion. After stirring is continued for one hour,diazotisation is complete. Sulphamic acid is added until no more nitriteis detected.

The diazonium suspension is stirred into the initially introducedsolution of the coupling component prepared above at 0° C., while, atthe same time, maintaining the pH in the coupling mixture at 7.0 withdilute sodium carbonate solution. After 3 hours, the temperature isallowed to rise to 20° C. and, after coupling is complete, the dyestuffis salted out. It is filtered off with suction, washed and, after addinga small amount of phosphate buffer, dried. The dyestuff of the formula##STR38## dyes cotton from a long liquor at an optimum dyeingtemperature of 50° C. and with good fixation yield in bluish red hues.

λ_(max). =541 nm in water.

Further red bifunctional reactive dyestuffs are obtained by reacting thecomponents mentioned in Examples 7-23 below.

             No. Diazo component naphthalenedisulphonic acid1-Amino-8-hydroxy-      Trihalogenotriazine      ##STR39##      Hue λ.sub.max (H.sub.2      O)      7     ##STR40##      ##STR41##      ##STR42##      ##STR43##      bluish red 540 nm      8     ##STR44##      ##STR45##      ##STR46##      ##STR47##      bluish red 546 nm      9     ##STR48##      ##STR49##      ##STR50##      ##STR51##      bluish red 546 nm      10     ##STR52##      ##STR53##      ##STR54##      ##STR55##      red 532 nm      11     ##STR56##      ##STR57##      ##STR58##      ##STR59##      red 533 nm      12     ##STR60##      ##STR61##      ##STR62##      ##STR63##      bluish red      13     ##STR64##      ##STR65##      ##STR66##      ##STR67##      bluish red      14     ##STR68##      ##STR69##      ##STR70##      ##STR71##      bluish red      15     ##STR72##      ##STR73##      ##STR74##      ##STR75##      bluish red      16     ##STR76##      ##STR77##      ##STR78##      ##STR79##      bluish red 541 nm      17     ##STR80##      ##STR81##      ##STR82##      ##STR83##      bluish red 541 nm      18     ##STR84##      ##STR85##      ##STR86##      ##STR87##      bluish red 541 nm      19     ##STR88##      ##STR89##      ##STR90##      ##STR91##      bluish red      20     ##STR92##      ##STR93##      ##STR94##      ##STR95##      bluish red      21     ##STR96##      ##STR97##      ##STR98##      ##STR99##      red      22     ##STR100##      ##STR101##      ##STR102##      ##STR103##      red      23     ##STR104##      ##STR105##      ##STR106##      ##STR107##      bluish red 544 nm

EXAMPLE 24

24.5 g of the azo compound of the formula ##STR108## are dissolved in340 ml of water at a pH of 7. After cooling to 0° to 2° C., the pH isbrought to 4.5 with dilute hydrochloric acid, and 4.3 ml of cyanuricfluoride are then immediately added dropwise over a period of 4 minutes.The pH is further maintained at 4.5 with 2N sodium carbonate solution.15 minutes later, the reaction is complete.

A solution of 18.5 g of the component of the formula ##STR109## in 50 mlof water adjusted to a pH of 5 is added and the pH in the reactionmixture is maintained at 5.0 to 5.5. After 2 hours, the temperature isallowed to rise to 20° C.

1 g of primary sodium phosphate is added, the pH is brought to 5.5 withdilute sodium hydroxide solution and the solution is then evaporated at35° to 40° C. in vacuo in a rotary evaporator. This gives an orangepowder which dyes cotton from a long liquor at an optimum dyeingtemperature of 40° to 60° C. and with an excellent fixation yield inreddish orange hues.

The dyestuff obtained has the formula ##STR110##

λ_(max). =498 nm in water.

Further orange-dyeing dyestuffs are obtained by condensing the followingazo components in an analogous manner with cyanuric fluoride andaminophenoxyalkyl β-sulphatoethyl sulphones.

           No. Azo component      ##STR111##      Hue λ.sub.max (H.sub.2      O)                                               25      ##STR112##      ##STR113##      orange      26     ##STR114##      ##STR115##      orange 485 nm      27     ##STR116##      ##STR117##      orange      28     ##STR118##      ##STR119##      orange 482 nm      29     ##STR120##      ##STR121##      orange 481 nm      30     ##STR122##      ##STR123##      orange      31     ##STR124##      ##STR125##      orange      32     ##STR126##      ##STR127##      scarlet      33     ##STR128##      ##STR129##      scarlet      34     ##STR130##      ##STR131##      orange      35     ##STR132##      ##STR133##      orange      35a     ##STR134##      ##STR135##      yellowish red      35b     ##STR136##      ##STR137##      yellowish red      35c     ##STR138##      ##STR139##      yellowish red 501 nm      35d     ##STR140##      ##STR141##      scarlet 501 nm

EXAMPLE 36

35.0 g of the coupling product of 2-aminonaphthalene-6,8-disulphonicacid onto 3-aminoacetanilide are dissolved in 600 ml of water at a pH of5.5 with heating to 50° C. The mixture is cooled to 0° C., and 7.7 ml ofcyanuric fluoride are added dropwise over a period of 5 to 10 min.During this time, the pH is maintained at 5.2 to 5.5 with dilute sodiumcarbonate solution.

When reaction is complete after about 10 to 15 minutes, a solution of30.5 g of the compound ##STR142## in 80 ml of water adjusted to a pH of5.5 is added dropwise, the pH is maintained at 5.5 to 5.7 with dilutesodium carbonate solution and the temperature is maintained at 0° to 5°C., later rising to 15° to 20° C.

The solution obtained, after addition of 1.5 g of phosphate buffer of pH6, is evaporated at 35° to 40° C. in vacuo or spray-dried.

The dyestuff of the formula ##STR143## dyes cotton from a long liquor atan optimum dyeing temperature of 50° C. in golden yellow hues.

λ_(max). =389 nm in water.

Further reddish yellow-dyeing dyestuffs are obtained by condensing thefollowing p-aminoazo compounds with cyanuric fluoride or cyanuricchloride and aminophenoxyalkyl β-sulphatoethyl sulphones.

            No. Azo component Trihalogenotriazine      ##STR144##      Hue λ.sub.max (H.sub.2      O)                                                37      ##STR145##      ##STR146##      ##STR147##      reddish yellow      38     ##STR148##      ##STR149##      ##STR150##      reddish yellow 389 nm      39     ##STR151##      ##STR152##      ##STR153##      reddish yellow 389 nm      40     ##STR154##      ##STR155##      ##STR156##      reddish yellow      41     ##STR157##      ##STR158##      ##STR159##      reddish yellow      42     ##STR160##      ##STR161##      ##STR162##      reddish yellow      43     ##STR163##      ##STR164##      ##STR165##      reddish yellow      44     ##STR166##      ##STR167##      ##STR168##      reddish yellow      45     ##STR169##      ##STR170##      ##STR171##      reddish yellow 386 nm      46     ##STR172##      ##STR173##      ##STR174##      reddish yellow      47     ##STR175##      ##STR176##      ##STR177##      orange

EXAMPLE 48

24.2 g of the aminoazopyrazolone of the formula ##STR178## (prepared bycoupling diazotised 2-amino-4-formylaminobenzenesulphonic acid onto 1-(4'-sulphophenyl) -3-carboxy-5-pyrazolone and hydrolysis using dilutesodium hydroxide solution) are dissolved in 600 ml of water in the formof the sodium salt. The mixture is cooled to 0° to 2° C., the pH isbrought to 5.0 with dilute hydrochloric acid and 4.0 ml of cyanuricfluoride are immediately added dropwise over a period of about 5minutes. During this, the pH is constantly maintained between 4.3 and4.6 with 2N sodium carbonate solution. When the reaction is completeafter 15 minutes, a neutral solution of 18.6 g of the compound of theformula ##STR179## in 100 ml of water is added at 0° to 5° C. Duringthis, the pH is maintained at 5.5 to 6 with 2N sodium carbonatesolution, and the temperature is allowed to rise to 20° C. after 2hours.

The dyestuff obtained of the formula ##STR180## dyes cotton from longliquor in greenish yellow hues with a high fixation yield.

EXAMPLE 49

Example 48 is repeated, except that the5-amino-2-sulphophenylazopyrazolone component is replaced by anequivalent amount of the corresponding4-amino-2-sulphophenylazopyrazolone, giving a dyestuff of the formula##STR181## which dyes cotton in more reddish yellow hues than that fromExample 48.

Further yellow dyestuffs having similar properties are obtained bycondensing the following aminophenylazopyrazolones with cyanuricfluoride and the aminophenoxyalkyl β-sulphatoethyl sulphones listed.

    __________________________________________________________________________     No.        Aminophenylazopyrazolone                                  ##STR182##    __________________________________________________________________________    50        ##STR183##                                  ##STR184##    51        ##STR185##                                  ##STR186##    52        ##STR187##                                  ##STR188##    53        ##STR189##                                  ##STR190##    54        ##STR191##                                  ##STR192##    55        ##STR193##                                  ##STR194##    56        ##STR195##                                  ##STR196##    __________________________________________________________________________

EXAMPLE 57

19.9 g of the azo compound of the formula ##STR197## prepared bycoupling diazotised 4-acetylamino-2-aminobenzenesulphonic acid onto1,4-dimethyl-6-hydroxy-5-amino-carbonyl-3-sulphomethyl-2-pyridone andhydrolysis of the acetylamino group in dilute sodium hydroxide solutionare dissolved in 400 ml of water at a pH of 5.0. After cooling to 0° C.,4.1 ml of cyanuric fluoride are run in, and the pH is maintained at 4.5with 2N sodium carbonate solution. Stirring under the same conditions iscontinued for 15 minutes, and a neutral solution of 21.3 g of thecomponent of the formula ##STR198## in 55 ml of water are then added.The pH is maintained at 5.2 to 5.3 with sodium carbonate solution andthe temperature is further maintained at 0° to 3° C., and thecondensation is completed by stirring overnight. The dyestuff is saltedout with potassium chloride, filtered off with suction and washed with15% strength potassium chloride solution.

It has the formula ##STR199##

λ_(max). =421 nm in water. and dyes cotton from a long liquor at anoptimum dyeing temperature of 40° to 50° C. in brilliant greenish yellowhues with a high fixation yield.

A dyestuff is obtained with a high fixation yield by condensing 17.3 gof the component of the formula ##STR200## dissolved in 110 ml of waterat a pH of 6 with 10% strength lithium hydroxide solution instead of the21.3 g of5-amino-2-[3-(β-sulphatoethylsulphonyl)-propoxy]-benzenesulphonic acidused above with the difluorotriazinylpyridone dyestuff. λ_(max) =421 nmin water.

Similar dyestuffs are obtained by reacting the components from Examples58 to 69 with one another using the procedure of Example 57.

            No. Azo component Trihalogenotriazine      ##STR201##      Hue λ.sub.max (H.sub.2      O)                                                58      ##STR202##      ##STR203##      ##STR204##      greenish yellow      59     ##STR205##      ##STR206##      ##STR207##      greenish yellow 420 nm      60     ##STR208##      ##STR209##      ##STR210##      greenish yellow 421 nm      61     ##STR211##      ##STR212##      ##STR213##      greenish yellow 421 nm      62     ##STR214##      ##STR215##      ##STR216##      greenish yellow 423 nm      63     ##STR217##      ##STR218##      ##STR219##      greenish yellow      64     ##STR220##      ##STR221##      ##STR222##      yellow      65     ##STR223##      ##STR224##      ##STR225##      yellow      66     ##STR226##      ##STR227##      ##STR228##      greenish yellow      67     ##STR229##      ##STR230##      ##STR231##      greenish yellow      68     ##STR232##      ##STR233##      ##STR234##      greenish yellow 421 nm      69     ##STR235##      ##STR236##      ##STR237##      yellow

EXAMPLE 70

40 g of1-amino-4-(2'-aminomethyl-4'-methyl-6'-sulphophenylamino)-anthraquinone-2-sulphonicacid are dissolved in 800 ml of water and 100 ml of acetone byneutralisation with about 45 ml of 2N sodium hydroxide solution at a pHof 7.

The mixture is cooled to 10° C. and a solution of 17.5 g of cyanuricchloride in 100 ml of acetone is added dropwise over a period of 15 to20 minutes. During the dropwise addition, the pH in the reaction mixtureis maintained at 6.0 to 7.0 with 2N sodium carbonate solution. Whensodium carbonate consumption has come to a standstill about 1 hour afterthe addition of cyanuric chloride, a neutralised solution of 39.7 g ofthe compound of the formula ##STR238## in 100 ml of water are run in at20° C., and the pH is maintained at 6.5 with sodium carbonate solution.After condensation is complete, the dyestuff is either salted out orisolated by evaporating the solution in vacuo at 35° to 40° C.,resulting in a salt-containing product. The dyestuff of the formula##STR239## can be used for printing or dyeing of cellulose fabric by thecontinuous method and produces clear reddish blue shades. Very goodfixation yields are obtained (λ_(max) =624 and 587 nm, in H₂ O).

EXAMPLE 71

53.1 g of1-amino-4-(3'-amino-5'-sulpho-2',4',6'-tri-methylphenylamino)-anthraquinone-2-sulphonicacid are dissolved in 530 parts of water at a pH of 6.

19.4 g of cyanuric chloride are dissolved in 100 ml of methyl ethylketone and the solution is poured onto 100 g of ice. The dyestuffsolution is then added dropwise to the cyanuric chloride suspension at0° to 10° C., and the pH in the reaction mixture is maintained at 4.5with 10% strength sodium carbonate solution. After conversion iscomplete, a neutralised solution of 47 g of the compound of the formula##STR240## in 130 ml of water is added at 20° to 25° C. and the pH ismaintained at 5.8 to 6.0 with sodium carbonate solution untilcondensation is complete. The dyestuff obtained of the formula##STR241## produces, by printing and continuous dyeing processes, oncotton clear, reddish blue shades with a very high fixation yield.

EXAMPLE 72

14.7 g of 1-amino-4-(3'-aminophenylamino)-anthraquinone-2,4'-disulphonicacid are dissolved in 250 ml of water at a pH of 5 and 0° to 5° C. 2.8ml of cyanuric fluoride are added dropwise to the solution of thedyestuff component over a period of 5 to 10 minutes and the pH ismaintained at 4.2 to 4.7 with 2N sodium carbonate solution. Stirring iscontinued for a short time, after which condensation to give thedifluorotriazinyl dyestuff is complete.

A neutralised solution of 13.2 g of the compound of the formula##STR242## in 50 ml of water is then slowly added to the solution of thereactive dyestuff component, while maintaining the pH at 5.0 to 5.6. ThepH is then maintained at 6.0 to 6.5 and the temperature is allowedgradually to increase to 20° C. over a period of 15 hours, after whichcondensation is complete. The dyestuff solution is then salted out overa period of 2 hours. The precipitated dyestuff of the formula ##STR243##is filtered off with suction and washed with salt solution until therun-off is clear. Drying in vacuo at 45° C. gives a product which can beused to dye and print cellulose fabric in blue hues and with a highfixation yield.

EXAMPLE 73

18.0 g of the component of the formula ##STR244## are brought to a pH of4.0 in 80 ml of water. 1.9 g of sodium fluoride are added to thesolution, and the mixture is cooled to 0° to 20° C. 4.2 ml of cyanuricfluoride are then run in with further cooling, and the pH is maintainedbetween 4.0 and 4.5 with sodium carbonate solution. About 15 minutesafter the cyanuric fluoride addition, conversion is complete. Thesolution is then brought to a pH of 4.5 to 5.0. A neutralised solutionof 19.0 g of1-amino-4-(3'-amino-2'-methylphenylamino)-anthraquinone-2,5'-disulphonicacid in 350 ml of water is then added dropwise to the reactive componentobtained over a period of 30 minutes. During this, the temperature inthe reaction solution is further maintained at 0° to 5° C. and the pH ismaintained at 6.0 to 6.5 with sodium carbonate solution. After 2 hours,the temperature is allowed gradually to increase to 10° C. over a periodof 15 hours. After condensation is complete, the dyestuff of the formula##STR245## is salted out from the solution with sodium chloride,filtered off with suction, washed with 20% strength sodium chloridesolution and dried at 45° C. in vacuo.

The dyestuff produces, on cotton, blue dyeings and prints with a highfixation yield.

Further blue anthraquinone dyestuffs having similar properties areobtained by condensing the anthraquinone components listed below of thegeneral formula ##STR246## with the trihalogenotriazines andsulphatoethylsulphonylalkoxyanilines by one of the methods describedabove.

    __________________________________________________________________________     No.        ##STR247##      Trihalogenotriazine                                   ##STR248##          Hue    λ.sub.max                                                              (H.sub.2    __________________________________________________________________________                                                             O)    74        ##STR249##                        ##STR250##                                   ##STR251##         blue   599 nm    75        ##STR252##                        ##STR253##                                   ##STR254##         blue   597 nm    76        ##STR255##                        ##STR256##                                   ##STR257##         reddish blue    77        ##STR258##                        ##STR259##                                   ##STR260##         blue    78        ##STR261##                        ##STR262##                                   ##STR263##         greenish blue    79        ##STR264##                        ##STR265##                                   ##STR266##         reddish blue    80        ##STR267##                        ##STR268##                                   ##STR269##         reddish blue    81        ##STR270##                        ##STR271##                                   ##STR272##         clear                                                             634 nm, 593 nm    82        ##STR273##                        ##STR274##                                   ##STR275##         clear blue    82a        ##STR276##                        ##STR277##                                   ##STR278##         clear                                                             635 nm, 593    __________________________________________________________________________                                                             nm

EXAMPLE 83

23.6 g of the component of the formula ##STR279## are brought to a pH of4.0 in 90 ml of water. 2.2 g of sodium fluoride are added to thesolution, and the mixture is cooled to 0° C. 4.9 ml of cyanuric fluorideare then run in, and the pH is maintained at 3.5 to 4.0 with 2N sodiumcarbonate solution. Stirring at 0° C. is continued for a short time,after which conversion is complete. The solution is brought to a pH of4.5 to 5.0.

0.05 mol of the copper complex ofN-(2-carboxy-5-sulphophenyl)-N'-(2'-hydroxy-3'-amino-5'-sulphophenyl)-ms-phenyl-formazandisodium salt is dissolved in 300 ml of water. After cooling to 0° to 5°C., the solution of the component prepared above is run in and the pH ismaintained at 5.5 to 6.0 by adding sodium carbonate solution. After 2hours, the temperature is allowed gradually to increase to 20° C. and,after condensation is complete, the dyestuff is salted out, filtered offwith suction and, after buffering at a pH of 6, dried at 45° C. invacuo.

The dyestuff obtained of the formula ##STR280## dyes cotton from a longliquor with very high fixation yields in blue hues.

λ_(max) =618 nm in water.

EXAMPLE 84

0.05 mol of the copper complex ofN-(2-carboxy-5-sulphophenyl)-N'-(2'-hydroxy-3'-amino-5'-sulphophenyl)-ms-phenylformazandisodium salt is dissolved in 250 ml of water. After cooling to 0° to 3°C., 4.9 ml of cyanuric fluoride are added dropwise over a period of afew minutes, while maintaining the pH at 5.5 to 6.0 with 10% strengthsodium carbonate solution. When condensation is complete after a shortperiod of additional stirring, a solution of 23 g of the component.##STR281## in 60 ml of water brought to a pH of 5 to 6 is added, and thepH is maintained at 5.5 to 6.0 with sodium carbonate solution. Aftercondensation is complete, the dyestuff is salted out with sodiumchloride, filtered off with suction and, after buffering to a pH of 6.0,dried at 45° C. in vacuo. It has the formula ##STR282## and dyes cottonfrom a long liquor with very high fixation yields in blue hues. λ_(max)=614 nm in water.

    __________________________________________________________________________                        Trihalogeno-                                  β-Sulphatoethylsulphonyl-                                                               λ.sub.ma                                                               x    No.       Aminoformazan    triazine  alkoxyaniline           Hue  (H.sub.2    __________________________________________________________________________                                                               O)    85 N-(2-Hydroxy-3-amino-5-sulpho- phenyl)-N'-(2'-carboxy-4'-sulpho-       phenyl)-ms-(2"-chloro-5"-sulpho- phenyl)-formazan, Cu                         ##STR283##                                   ##STR284##             blue    86 N-(2-Hydroxy-5-amino-3-sulpho- phenyl)-N'-(2',5'-disulphophenyl)-       ms-phenyl-formazan, Cu complex                         ##STR285##                                   ##STR286##             blue    87  2-(2-Carboxy-4-aminophenyl)-N'- (2'-hydroxy-5'-methylsulfonyl-3'-       sulphophenyl)-ms-(2"-sulpho- phenyl)-formazan, Cu complex                         ##STR287##                                   ##STR288##             blue    88 N-(2-Carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3',5'-disulphophenyl)-       ms-(3"-aminophenyl)-formazan, Cu complex                         ##STR289##                                   ##STR290##             greenish blue    89 N-(4-Amino-2-sulphophenyl)-N'-(2'- hydroxy-4'-sulphophenyl)-ms-(4"-       chloro-3"-sulphophenyl)-formazan, Cu complex                         ##STR291##                                   ##STR292##             blue    90 N-(2-Hydroxy-3-amino-5-sulpho- phenyl)-N'-(2'-hydroxy-4'-sulpho-       phenyl)-ms-(2'-sulphophenyl), Cu complex                         ##STR293##                                   ##STR294##             navy    91 N-(2-Carboxy-5-sulphophenyl)-N'- 2-hydroxy-5'-amino-3'-sulpho-       phenyl)-ms-(4"-sulphophenyl)- formazan, Cu complex                         ##STR295##                                   ##STR296##             blue    92 N-(2-Carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho-       phenyl)-ms-phenylformazan, Cu complex                         ##STR297##                                   ##STR298##             blue    93 N-(2-Carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho-       phenyl)-ms-phenylformazan, Cu complex                         ##STR299##                                   ##STR300##             blue    94 N-(2,4-Disulphophenyl)-N'-(2'- hydroxy-4,6-disulphophenyl)-ms-       (3"-aminophenyl)-formazan, Cu complex                         ##STR301##                                   ##STR302##             blue    95 N-(2-Carboxy-5-sulphophenyl)-N'- (2'-hydroxy-4'-methylsulphonyl-6'-       sulphophenyl)-ms-(3"-amino- phenyl)-formazan, Cu complex                         ##STR303##                                   ##STR304##             blue    96 N-(2-Hydroxy-5-sulphophenyl)-N'- (2'-hydroxy-3',5'-disulphophenyl)-       ms-(4"-aminophenyl)-formazan, Cu complex                         ##STR305##                                   ##STR306##             blue    97 N-(2-Carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho-       phenyl)-ms-(4"-methyl-3"-bromo- phenyl)-formazan, Cu                         ##STR307##                                   ##STR308##             blue    98 N-(2-Carboxy-4-aminophenyl)-N'- (2'-hydroxy-4'-sulphonaphth-1'-yl)-       ms-(2"-sulphophenyl)-formazan, Cu complex                         ##STR309##                                   ##STR310##             blue    98a       N-(2-Carboxy-4-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho-       phenyl)-ms-phenylformazan, Cu complex                         ##STR311##                                   ##STR312##             blue    98b       N-(2-Carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho-       phenyl)-ms-phenylformazan, Cu complex                         ##STR313##                                   ##STR314##             blue 618 nm    98c       N-(2-Carboxy-5-sulphophenyl)-N'- (2'-hydroxy-3'-amino-5'-sulpho-       phenyl)-ms-(2"-sulphophenyl)- formazan, Cu complex                         ##STR315##                                   ##STR316##             blue    98d       N-(2-carboxy-5-sulphophenyl)-N'- (2'-hydroxy-5'-amino-3'-sulpho-       phenyl-ms-phenylformazan, Cu complex                         ##STR317##                                   ##STR318##             blue    __________________________________________________________________________

EXAMPLE 99

A neutralised solution of 15.5 g of the component of the formula##STR319## and 1.6 g of sodium fluoride in 60 ml of water is cooled to0° to 2° C. 5.5 g of cyanuric fluoride are run in and the pH ismaintained between 3.5 and 4.0 with 2N sodium carbonate solution. Aftercondensation is complete, the pH is brought to 5.0.

32 g of the copper phthalocyanine component of the formula ##STR320##prepared by the procedure given in European Patent 0,073,267 aredissolved in 300 ml of water at a pH of 7.0 to 7.5. The solution of theabove condensation product is then run into the dyestuff component at 0°to 5° C., and the pH in the reaction mixture is maintained at 7.0 to7.5. After 3 hours, the temperature is allowed gradually to increase to20° C. and the pH is further kept constant. After conversion iscomplete, the product obtained is salted out f rom the solution,filtered off with suction, buffered at a pH of 6.0 with a small amountof phosphate solution and dried at 45° C. in vacuo. The dyestuff has theformula ##STR321## and dyes cotton from a long liquor and by theconventional continuous processes in greenish blue hues. λ_(max) =668nm, 627 nm in water.

EXAMPLE 100

28.3 g of the copper phthalocyanine compound of the formula ##STR322##(prepared by condensing copper phthalocyaninetetrasulphonylchloride/sulphonic acid with monoacetylethylenediamine, followed byhydrolysis by the procedure given in German Offenlegungsschrift1,644,681, Example 2) are dissolved in 380 ml of water at a pH of 8.5.The solution is added dropwise over a period of 30 minutes to asuspension obtained by pouring a solution of 5.6 g of cyanuric chloridein 45 ml of acetone onto 45 g of ice.

The pH in the reaction mixture is maintained at 7.0 to 7.5 by adding 2Nsodium hydroxide solution and the temperature is maintained at 0° to 5°C. Stirring is continued for 1 hour, after which the solution isclarified and 10.3 g of2-[3-(2-sulphatoethylsulphonyl)-propoxy)-5-aminobenzenesulphonic acidare added to the filtrate in portions.

During the addition and later on, the pH in the reaction mixture ismaintained at 6.0 to 6.5 and after the addition the temperature isincreased to 20° to 25° C. After condensation is complete, the dyestuffis salted out from the solution with sodium chloride, filtered off withsuction and dried at 40° to 50° C. in vacuo. The dyestuff has theformula ##STR323## and produces, on cellulose fabric, greenish bluedyeings and prints with a high yield.

λ_(max) =668 run, 629 nm in H₂ O.

EXAMPLE 101

31.2 g of the copper phthalocyanine compound of the formula ##STR324##prepared by condensing copper phthalocyanine-tetrasulphonylchloride/sulphonic acid with 3-aminoacetanilide and ammonia, followed byhydrolysis of the acetylamino group in dilute sodium hydroxide solutionat 75° C., are dissolved in 420 ml of water at a pH of 7. The solutionis added dropwise over a period of 30 minutes to a suspension preparedfrom a solution of 5.9 g of cyanuric chloride in 50 ml of acetone and 50g of ice, and the temperature in the reaction mixture is maintained at0° to 3° C. and the pH is maintained at 4.0 to 4.5 by metering in 2Nsodium carbonate solution. 30 minutes after addition has ended, theresulting solution is clarified, and a neutral solution of 10.9 g of4-[3-(2-sulphatoethylsulphonyl)propoxy)-aniline in 200 ml of water isadded. By further addition of sodium carbonate, the condensationreaction is carried out at a pH of 6.0 to 6.5, during which thetemperature is brought to 20° to 25° C. The dyestuff obtained isisolated either by evaporation in vacuo or by salting out and filteringoff with suction followed by drying.

It has the formula ##STR325##

λ_(max) =668 nm, 629 nm in water and dyes and prints cotton, byprocesses known for reactive dyestuffs, in a high yield in greenish bluehues which have good fastness properties.

Further phthalocyanine reactive dyestuffs are obtained by condensing thephthalocyanine components, trihalogenotriazines andβ-sulphatoethylsulphonylalkoxyanilines indicated in the list below withone another by one of the methods described above.

      No. Phthalocyanine component Trihalogenotriazine β     Sulphatoethylsulphonylalkoxyaniline Hue λ.sub.max (H.sub.2     O)             102      ##STR326##      ##STR327##      ##STR328##      greenish blue      103     ##STR329##      ##STR330##      ##STR331##      greenish blue      104     ##STR332##      ##STR333##      ##STR334##      bluish green      105     ##STR335##      ##STR336##      ##STR337##      bluish green      106     ##STR338##      ##STR339##      ##STR340##      bluish green      107     ##STR341##      ##STR342##      ##STR343##      greenish blue      108     ##STR344##      ##STR345##      ##STR346##      greenish blue      109     ##STR347##      ##STR348##      ##STR349##      greenish blue      110     ##STR350##      ##STR351##      ##STR352##      greenish blue      111     ##STR353##      ##STR354##      ##STR355##      greenish blue      112     ##STR356##      ##STR357##      ##STR358##      greenish blue      113     ##STR359##      ##STR360##      ##STR361##      greenish blue      113a     ##STR362##      ##STR363##      ##STR364##      turkis 668 nm, 627 nm

EXAMPLE 114

36.7 g of the amino-disazo compound prepared in the known manner of theformula ##STR365## are dissolved in 400 ml of water at a pH of 6.0.After cooling the solution to 0° C., 5.0 ml of cyanuric fluoride areswiftly added dropwise and the pH is maintained at 4.5 to 5.0 with 2Nsodium carbonate solution.

After this first condensation step is complete, 19.1 g of4-[3-(2-sulphatoethylsulphonyl)- propoxy)-aniline are added and the pHis maintained at 5.5 to 6.0 with sodium carbonate solution. Stirring at0° to 5° C. is continued for 2 hours, and the temperature is thenallowed to rise to 20° C. with further pH control. The dyestuff obtainedof the formula ##STR366## is salted out with sodium chloride, filteredoff with suction and, after buffering at a pH of 6, dried at 45° C. invacuo. It dyes cotton, by the processes known for reactive dyestuffs,with a high yield in brown hues.

EXAMPLE 115

If the compound of the formula ##STR367## is condensed instead of theaminodisazo compound from Example 114 with cyanuric fluoride and thenwith the compound of the formula ##STR368## a dyestuff of the formula##STR369## is obtained, which dyes cotton also with a high yield inbrown hues.

Further brown reactive dyestuffs are obtained by condensing thefollowing components.

      No. Aminodisazo compound Trihalogenotriazine β     Sulphatoethylsulphonylalkoxyaniline Hue            116      ##STR370##      ##STR371##      ##STR372##      brown      117     ##STR373##      ##STR374##      ##STR375##      brown      118     ##STR376##      ##STR377##      ##STR378##       brown      119     ##STR379##      ##STR380##      ##STR381##      orange-brown

EXAMPLE 120

50.3 g of the aminoazo compound of the formula ##STR382## are dissolvedin 400 ml of water at a pH of 6. The solution is cooled to 0° to 2° C.,and 9.3 ml of cyanuric fluoride are added dropwise over a period of afew minutes. During this operation, the pH is maintained at 4.5 with 2Nsodium carbonate solution, and stirring of the mixture under the sameconditions is continued for a short period. When sodium carbonateconsumption has come to a standstill, a solution of 35.4 g of4-[3-(2-sulphatoethylsulphonyl)-propoxy)-aniline in 180 ml of waterbrought to a pH of 6 with 10% strength lithium hydroxide solution is runin, and the pH in the reaction mixture is maintained at 5.5 to 6.0.After 3 hours, the temperature is allowed gradually to increase to 20°C., and the dyestuff obtained of the formula ##STR383## is isolated bysalting it out and filtering it off with suction. Gentle drying gives apowder which dyes cotton by the customary methods with a high yield inscarlet hues.

EXAMPLE 121

If the aminoazo compound in Example 120 is replaced by an equivalentamount of the isomeric compound ##STR384## and condensed with cyanuricfluoride and, in a second step, with a compound of the formula##STR385## the dyestuff of the formula ##STR386## is obtained, whichdyes cotton in reddish orange hues with high fixation yields.

Further reactive dyestuffs based on aminoazonaphthol compounds areobtained by condensing the components below.

      No. Aminoazonaphthol component Trihalogenotriazine β     Sulphatoethylsulphonylalkoxyaniline Hue            122      ##STR387##      ##STR388##      ##STR389##      orange      123     ##STR390##      ##STR391##      ##STR392##      orange      124     ##STR393##      ##STR394##      ##STR395##      yellowish red      125     ##STR396##      ##STR397##      ##STR398##      orange      126     ##STR399##      ##STR400##      ##STR401##      brown      127     ##STR402##      ##STR403##      ##STR404##      brown

EXAMPLE 126

18.8 g of 2,4-diaminobenzenesulphonic acid are condensed in 100 ml ofwater at 0° to 3° C. and a pH of 4.5 with 18.5 g of cyanuric chloride.105 ml of 10% strength hydrochloric acid are added, 6.9 g of NaNO₂ in 60ml of water are then added and the mixture is stirred untildiazotisation is complete.

A neutral aqueous solution of 36.1 g of1-acetylamino-8-hydroxynaphthalene-4,6-disulphonic acid is run into thediazo suspension, and the pH is brought to 6.5 to 7.0 with sodiumcarbonate solution in order to effect coupling. The temperature isallowed to rise to 10° C. over a period of 2 hours and to 20° C. over afurther 2 hours. After coupling is complete, 34 g of4-[3-(2-sulphatoethylsulphonyl)-propoxy)-aniline are introduced inportions into the batch, and the pH is further maintained at 6.5. Whencondensation is complete, the dyestuff obtained of the formula##STR405## is salted out, filtered off with suction, and dried at 45° C.in vacuo. It dyes cotton in red hues with a high fixation yield.

Similar dyestuffs are obtained by condensing the components indicated inthe list below with one another.

      No. Diaminobenzenesulphonic acid Trihalogenotriazine Coupling component     β     Sulphatoethylsulphonylalkoxyaniline Hue             129      ##STR406##      ##STR407##      ##STR408##      ##STR409##      red      130     ##STR410##      ##STR411##      ##STR412##      ##STR413##      red      131     ##STR414##      ##STR415##      ##STR416##      ##STR417##      red      132     ##STR418##      ##STR419##      ##STR420##      ##STR421##      red      133     ##STR422##      ##STR423##      ##STR424##      ##STR425##      red      134     ##STR426##      ##STR427##      ##STR428##      ##STR429##      red      135     ##STR430##      ##STR431##      ##STR432##      ##STR433##      red

EXAMPLE 136

According to Example 99, 21.0 g of the component of the formula##STR434## are condensed with 7.4 g of cyanuric fluoride in 80 ml ofwater in the presence of 2.1 g of sodium fluoride. The solution obtainedof the condensation product is run into a solution of 31 g of the azocompound of the formula ##STR435## in 300 ml of water brought to a pH of7 and cooled to 0° to 5° C., and the pH in the mixture is maintained at6.5 with dilute sodium carbonate solution. After 3 hours, thetemperature is gradually increased to 20° C. After condensation iscomplete, the dyestuff is isolated by salting it out and filtering itoff with suction and, after buffering to a PH of 6.5, it is dried at 45°C. in vacuo. It has the formula and dyes cotton from a long liquor inbluish red hues with a high fixation yield.

Similar red dyestuffs are obtained by reacting the following components.

    __________________________________________________________________________    No.       Azo component                 Trihalogenotriazine                                               2-Sulphatoethylsulphonylalkoxya                                               niline    __________________________________________________________________________    137        ##STR436##                                      ##STR437##                                                ##STR438##    138        ##STR439##                                      ##STR440##                                                ##STR441##    139        ##STR442##                                      ##STR443##                                                ##STR444##    140        ##STR445##                                      ##STR446##                                                ##STR447##    __________________________________________________________________________

EXAMPLE 141

According to Example 99, 21 g of5-amino-2-[3-(2-sulphatoethylsulphonyl)-propoxy]-benzenesulphonic acidin 80 ml of water and 2.1 g of sodium fluoride are condensed with 7.5 gof cyanuric fluoride.

22.1 g of the triphendioxazine compound of the formula ##STR448## aredissolved in 300 ml of water by adding sodium hydroxide solution at a pHof 11.5-12.

This solution and that of the reactive components prepared above areadded dropwise simultaneously to 80 ml of initially introduced icewater, and the pH in the reaction mixture is maintained at 8-8.5 with 2Nsodium hydroxide solution and the temperature is further maintained at0°-2° C. After several hours, conversion is complete. The temperature isallowed to rise to 20° C. overnight. The dyestuff is salted out,filtered off with suction and, after buffering to a pH of 6.7, dried at45° C. in vacuo. It has the formula ##STR449## and dyes cotton by thecustomary methods in strong blue shades with high fixation yields.

EXAMPLE 142

27 g of the triphendioxazine compound of the formula ##STR450## aredissolved in 1,000 ml of water by bringing the pH to 7.0 with 10%strength lithium hydroxide.

The mixture is cooled to 0° to 5° C., and a solution of 9.2 g ofcyanuric chloride in 50 ml of acetone is added dropwise.

The pH in the reaction mixture is maintained at 6.0 to 6.5 by dropwiseaddition of lithium hydroxide solution. To complete the reaction, thetemperature is raised to 20° C. over a period of 2 hours and the pH isfurther maintained within the above limits until consumption of theneutralising agent has come to a standstill. A neutralised solution of20.8 g of5-amino-2-[3-(β-sulphatoethylsulphonyl)-propoxy)-benzenesulphonic acidin 80 ml of water is then added to the primary condensation product andthe pH is further maintained at 6.0 to 6.5 with lithium hydroxide.

The dyestuff obtained of the formula ##STR451## dyes cotton from a longliquor at an optimum dyeing temperature of 70° C. to 80° C. in stronglyreddish blue hues.

Further triphendioxazine reactive dyestuffs are obtained by a procedureanalogous to that for Examples 141 and 143 by condensing the followingcomponent:

      No. Triphendioxazine Trihalogenotriazine β     Sulphatoethylsulphonylalkoxyaniline Hue            143      ##STR452##      ##STR453##      ##STR454##      blue      144     ##STR455##      ##STR456##      ##STR457##      blue      145     ##STR458##      ##STR459##      ##STR460##      blue      145a     ##STR461##      ##STR462##      ##STR463##      blue      146     ##STR464##      ##STR465##      ##STR466##      bluish red      147     ##STR467##      ##STR468##      ##STR469##      reddish blue      148     ##STR470##      ##STR471##      ##STR472##      reddish blue

EXAMPLE 149

35.2 g of the known compound ##STR473## are dissolved in 350 ml ofwater, and the pH of the solution is brought to 5.0. The solution iscooled to 0° C., 7.4 g of cyanuric fluoride are added dropwise and thepH is maintained at 4.5 with 2N sodium carbonate solution.

After conversion is complete, a neutralised solution of 23. 0 g of5-amino-2- [3- (2-sulphatoethylsulphonyl) -propoxy)-benzenesulphonicacid in 70 ml of water is added, and the pH is maintained at 6. 0 with2N sodium carbonate solution, during which the temperature is firstmaintained at 0° to 5° C. for 4 hours and then gradually increased to20° C.

After condensation is complete, the dyestuff, after buffering to a pH of6, is isolated either directly by spray-drying or by salting out,filtering off with suction and vacuum-drying at 40° C. The dyestuff hasthe formula ##STR474## and dyes cotton by the dyeing techniquescustomary for reactive dyestuffs in navy hues with high yields.

Further similar reactive dyestuffs which dye cellulose fibres navy toblack are obtained by condensing the aminodisazo components indicated inthe list below of the general formula ##STR475## with thetrihalogenotriazines and β-sulphatoethylsulphonylalkoxyanilines.

    __________________________________________________________________________    Aminodisazo component    No.       D.sub.1       D.sub.2   Trihalogenotriazine                                          β-Sulphatoethylsulphonylalkoxya                                          niline              Hue    __________________________________________________________________________    150        ##STR476##                      ##STR477##                                ##STR478##                                           ##STR479##         navy    151        ##STR480##                      ##STR481##                                ##STR482##                                           ##STR483##         navy    152        ##STR484##                      ##STR485##                                ##STR486##                                           ##STR487##         navy    152a        ##STR488##                      ##STR489##                                ##STR490##                                           ##STR491##         navy    153        ##STR492##                      ##STR493##                                ##STR494##                                           ##STR495##         navy    154        ##STR496##                      ##STR497##                                ##STR498##                                           ##STR499##         greenish                                                              black    155        ##STR500##                      ##STR501##                                ##STR502##                                           ##STR503##         navy    156        ##STR504##                      ##STR505##                                ##STR506##                                           ##STR507##         navy    157        ##STR508##                      ##STR509##                                ##STR510##                                           ##STR511##         navy    158        ##STR512##                      ##STR513##                                ##STR514##                                           ##STR515##         black    159        ##STR516##                      ##STR517##                                ##STR518##                                           ##STR519##         navy    160        ##STR520##                      ##STR521##                                ##STR522##                                           ##STR523##         black    __________________________________________________________________________

EXAMPLE 161

50 mmol of the known copper complex compound of the formula ##STR524##are dissolved in 600 ml of water at a pH of 6.5. The mixture is cooledto 0°-30° C., and 7.4 g of cyanuric fluoride are added dropwise to thissolution over a period of a few minutes. During the dropwise addition,the pH is maintained at 4.5-5.0 with 2N sodium carbonate solution.Stirring is continued for another quarter of an hour, after which aneutralised solution of 23.0 g of the compound of the formula ##STR525##in 100 ml of water is added to the primary condensation product, and thepH in the reaction mixture is maintained at 5.0-6.0 with sodiumcarbonate solution. When sodium carbonate consumption has gradually cometo a standstill, the temperature is allowed to rise to 20° C. Afterconversion is complete, the dyestuff of the formula ##STR526## is saltedout, isolated, and, after buffering to a pH of 6, dried at 45° C. invacuo.

The product dyes cellulose fibres, by the dyeing techniques customaryfor reactive dyestuffs, in navy hues with a very high fixation yield.

EXAMPLE 162

A neutralised solution of 24.1 g of the component of the formula##STR527## and 2.4 g of sodium fluoride in 100 ml of water is condensedanalogously to Example 99 with 8.6 g of cyanuric fluoride.

The solution obtained is run in at 0°-2° C. to a neutral solution of 50mmol of the known copper complex compound of the formula ##STR528## andthe pH in the reaction mixture is maintained at 5-6 with 2N sodiumcarbonate solution. When sodium carbonate uptake subsides after a fewhours, the temperature is slowly raised to 20° C.

After condensation is complete, the dyestuff of the formula ##STR529##is salted out, isolated and dried at 45° C. in vacuo. It dyes cellulosefibres, by the drying techniques customary for reaction dyestuffs, inblue hues.

Further reactive dyestuffs which dye cotton by the customary dyeingtechniques with a very high yield are obtained by condensing the knowncopper complex compounds indicated in the list below with thetrihalogenotriazines and the β-sulphatoethylsulphonylalkoxyanilinesusing the procedures described in Examples 161 or 162.

      No. Copper complex compound Trihalogenotriazine β     Sulphatoethylsulphonylalkoxyaniline hue            163      ##STR530##      ##STR531##      ##STR532##      navy      164     ##STR533##      ##STR534##      ##STR535##      navy      165     ##STR536##      ##STR537##      ##STR538##      reddish navy      166     ##STR539##      ##STR540##      ##STR541##      navy      167     ##STR542##      ##STR543##      ##STR544##      navy      168     ##STR545##      ##STR546##      ##STR547##      dark blue      169     ##STR548##      ##STR549##      ##STR550##      green      170     ##STR551##      ##STR552##      ##STR553##      red-violet      171     ##STR554##      ##STR555##      ##STR556##      navy      172     ##STR557##      ##STR558##      ##STR559##      navy      173     ##STR560##      ##STR561##      ##STR562##      blue-violet

EXAMPLE 174

50 mmol of the 1:2 chromium complex of the formula ##STR563## which canbe obtained by coupling diazotised 5-nitro-2-aminophenol with1-amino-8-hydroxynaphthalene-3,6-disulphonic acid, followed byconversion into the 1:2 Cr complex, are dissolved in 750 parts of waterat a pH of 7, and a solution prepared, using the procedure of Example99, from 48.2 g of5-amino-2-[3-(2-sulphatoethylsulphonyl)-propoxy]-benzenesulphonic acidand 15.5 g of cyanuric fluoride and containing the compound ##STR564##is added. The pH is maintained at 6-6.5 and the temperature ismaintained at 20°-25° C. After condensation is complete, the reactivedyestuff obtained is salted out, filtered off with suction and, afterbuffering to a pH of 6.5, gently dried in vacuo. Using the dark powderobtained, cotton is dyed in greenish grey hues.

If a 1:1 mixture of the chromium complex and the corresponding cobaltcomplex is used instead of the abovementioned pure chromium complex, adyestuff mixture is isolated which dyes cotton in neutral grey or blackhues having good light fastness properties.

EXAMPLE 175

50 mmol of the Co complex of the formula ##STR565## are dissolved in 800parts by volume of water at a pH of 6, and the solution is cooled to0°-5° C. 14.9 g of cyanuric fluoride are added dropwise with vigorousstirring, and the pH is maintained at 4.5-5.0 with 2N sodium carbonatesolution. After the primary condensation is complete, a neutral solutionis added which contains 23.0 g of the component ##STR566## and 18.6 g ofthe component of the formula ##STR567## in 150 ml of water. The pH ismaintained at 5.5-6.0, and the temperature is allowed to rise to 20° C.after 2 hours. When condensation is complete, the reactive dyestuffobtained is salted out, filtered off with suction and dried at 45° C. invacuo. The powder obtained dyes cotton, by the techniques customary forreactive dyestuffs, with a high yield in brown hues which have goodlight fastness properties.

EXAMPLE 176

50 mmol of the triphendioxazine compound of the formula ##STR568## aredissolved in 900 ml of water at a pH of 6. 14.9 g of cyanuric fluorideare added dropwise to the solution at 0°-3° C. and the pH is maintainedat 4.5-5.0 with 2N sodium carbonate solution.

Stirring is continued for a short period, after which a neutral solutionof 46.1 g of5-amino-2-[3-(β-sulphatoethylsulphonyl)-propoxy]-benzenesulphonic acidin 160 ml of water is added to the primary condensation product, and thepH is maintained at 6.0. After condensation has been completed bygradually increasing the temperature to 20° C., the dyestuff of theformula ##STR569## is salted out, isolated and dried.

It dyes cellulose fibres in greenish blue hues.

EXAMPLE 177

21.9 g of 1-(4-benzoylamino)-8-hydroxynaphthalene-3,6-disulphonic acidare dissolved in 250 ml of water at a pH of 5.5. After cooling thesolution to 0°-3° C., 7.1 g of cyanuric fluoride are swiftly addeddropwise, and the pH in the reaction mixture is maintained at 4.5 withdilute sodium carbonate solution. Stirring is continued for a shortperiod, after which a neutral solution of 22.0 g of5-amino-2-[3-(β-sulphatoethylsulphonyl)-propoxy]-benzenesulphonic acidin 80 ml of water cooled to 0° C. is added, and the pH is maintained at5.5-6.0 overnight. After condensation is complete, a diazonium saltsuspension obtained in the usual manner by diazotisation of 8.7 g of2-aminobenzenesulphonic acid is added, and coupling is completed byaddition of sodium carbonate at a pH of 6.5-7 first at 0° C. for severalhours and later on with an increase to 20° C. The dyestuff obtained ofthe formula ##STR570## is isolated and dried. It produces on cotton,from a long liquor, strong red dyeings having good light and wetfastness.

EXAMPLE 178

25.7 g of the triazole of the formula ##STR571## prepared by theprocedure given in European Patent 0,013,879 are dissolved in 700 ml ofwater at a pH of 6.5. The solution is cooled to 0° C., and 6.9 g ofcyanuric fluoride are slowly added dropwise. The pH is maintained at6.0-6.5 with sodium bicarbonate solution. When the reaction is completeafter a few minutes, a neutral, cooled solution of 21.8 g of5-amino2-[3-(β-sulphatoethylsulphonyl)-propoxy]-benzenesulphonic acid in80 ml of water is added, and the pH is further maintained at 6.5 withsodium carbonate solution.

After 2 hours, the temperature is allowed to rise to 20° C. 3.7 g ofsodium nitrite are added, and 20 ml of 28% strength hydrochloric acidare run in. After one hour of after-reaction, any excess nitrous accidis destroyed with sulphamic acid. 6.5 g of barbituric acid are sprinkledin and coupling is carried out first at a PH of 5 by adding sodiumacetate and later on at a pH of 5.5-6 using sodium carbonate. Aftercoupling is complete, the dyestuff is isolated and dried at 40° C. invacuo. It has the formula ##STR572## and dyes cotton in brilliant yellowshades.

Similar yellow dyestuffs are obtained by using the following couplingcomponents instead of barbituric acid:

2,6-dihydroxypyridine-4-carboxylic acid

1-(4-sulphophenyl)-3-methyl-5-pyrazolone

1-(4-sulphophenyl)-5-pyrazolone-3-carboxylic acid

1,4-dimethyl-2-hydroxy-6-pyridone-5-carboxamide

1,4-dimethyl-2-hydroxy-3-sulphomethyl-6-pyridone-5-carboxamide

N-(2'-methoxy-5'-methyl-4'-sulphophenyl) aceto acetamide

N-(2',5'-dimethoxy-4'-sulphophenyl ) aceto acetamide

1-phenyl-3-methyl-5-aminopyrazole

1-(6,8-disulphonaphth-2-yl)-3-methyl-5-pyrazolone

1,4-dimethyl-2-hydroxy-5-cyano-6-pyridone

EXAMPLE 179

260 g of powdered potassium hydroxide are dissolved in 2,000 ml of1,3-propanediol at 70° C. 500 g of 1-chloro-2-nitrobenzene are addeddropwise to the solution at 50° C., the mixture is heated at 50° C. for5 hours and then at 60° C. until conversion is complete. The batch ispoured onto 6,000 ml of ice water, the precipitated oil is separatedoff, washed several times with water and dried in a rotary evaporator.

457 g of the oil obtained are dissolved in 460 ml of pyridine. Asolution of 445 g of p-toluenesulphonyl chloride in 450 ml of pyridineis added dropwise to this mixture at 5°-15° C. over a period of 1 hour.After stirring at 0°-5° C. for 3 hours, the precipitated crystals arefiltered off with suction, washed with 1.8 l of cold methanol at 0°-5°C., then with 2 l of water and dried at 50° C. in vacuo.

475.0 g of the tosyl ester obtained of the formula ##STR573## are heatedtogether with 115 g of 2-mercaptoethanol and 215 g of potassiumcarbonate in 1,200 ml of acetonitrile at 83° C. with reflux for 4 hours.The mixture is then taken up in 6 l of water, the precipitated yellowoil is separated off and washed with water. 355 g of the1-nitro-2-(3-(2-hydroxyethylthio)-propoxylbenzene obtained are oxidisedto the sulphone in 2,000 ml of water with 250 ml of 35% strength H₂ O₂in a known manner at 55°-60° C. after addition of 4 g of sodiumtungstate.

The product obtained is filtered off with suction, washed with ice waterand dried at 55° C. in vacuo.

373 g of the 1-nitro-2-[3-(2-hydroxyethylsulphonyl)-propoxy]-benzeneobtained are hydrogenated catalytically at 60° C. in 1,600 ml ofmethanol in the presence of 7 g of Raney nickel under a hydrogenpressure of 30 bar. After filtering off nickel while hot, evaporation ofthe filtrate gives the amine of the formula ##STR574## in the form ofbrownish crystals.

¹ H-NMR (D₆ -DMSO)

    ______________________________________    δ = 2.08-2.2                  ppm          (2H, m)    δ = 3.26                  ppm          (2H, t)    δ = 3.36                  ppm          (2H, t)    δ = 3.82                  ppm          (2H, q)    δ = 4.02                  ppm          (2H, t)    δ = 5.14                  ppm          (1H, t)    δ = 6.45-6.50                  ppm          (1H, m)    δ = 6.60-6.68                  ppm          (2H, m)    δ = 6.72                  ppm          (1H, m)    ______________________________________

250 g of the above amine are added dropwise as a hot melt of 60° C. intoa mixture at 0°-2° C. of 610 ml of 96% pure sulphuric acid and 24 ml ofwater over a period of 11/2 hours. Stirring at 0° C. is continued for 1hour, the solution is poured into 3,000 g of ice and 1,500 ml of water,the suspension is stirred for another hour, the crystals are filteredoff with suction and washed free of sulphuric acid with 2 l ofisopropanol. They are dried at 45° C. in vacuo.

The product has the formula ##STR575##

¹ H-NMR (D₆ -DMSO)

    ______________________________________    δ = 2.13-2.26                  ppm          (2H, m)    δ = 3.40-3.48                  ppm          (4H, m)    δ = 4.13-4.23                  ppm          (4H, m)    δ = 7.01-7.06                  ppm          (1H, m)    δ = 7.18                  ppm          (1H, m)    δ = 7.33-7.45                  ppm          (2H, m)    δ = ˜9.6                  ppm          (broad)    ______________________________________

If 100 g of the above1-amino-2-[-3-(2-hydroxyethylsulphonyl)-propoxyl-benzene are addeddropwise as a melt into 300 ml of 20% strength oleum at 0°-2° C.,stirring is continued for some time until no more change can be detectedin the solution by chromatography, the mixture is poured onto 2.6 kg ofice, excess sulphuric acid is removed by introducing 558 g of calciumcarbonate up to a pH of 4.5, the calcium sulphate is filtered off withsuction and washed with 1 l of water, and the filtrate is concentratedto about 500 ml, a solution of the product of the formula ##STR576##whose content is determined by titration with sodium nitrite isobtained.

EXAMPLE 180

313 g of 1-[2-(2-hydroxyethoxy)-ethoxy]-4-nitrobenzene are heated in 930ml of thionyl chloride and 5 ml of dimethylformamide with reflux for 3hours. The solution is poured onto 3.5 kg of ice and 3.5 1 of water, thecrystalline white precipitate is filtered off with suction and freedfrom acid residues by washing with cold water. The product can be driedat 55° C. in vacuo.

330 g of 1-[2-(2-chloroethoxy)-ethoxy]-4-nitrobenzene are reacted with130 g of 2-mercaptoethanol and 235 g of potassium carbonate by refluxingin 900 ml of acetonitrile. After complete conversion, the mixture ispoured into 3 l of water, the pH is brought to 6-7 with dilute sulphuricacid, and, after addition of 4 g of sodium tungstate, the thio ether isoxidised in the known manner at 55°-60° C. using 280 g of 35% strengthhydrogen peroxide. The product obtained of the formula ##STR577## isdried at 50° C. in vacuo. M.p. 58°-59° C.

¹ H-NMR (D₆ -DMSO)

    ______________________________________    δ = 3.28                  ppm          (2H, t)    δ = 3.44                  ppm          (2H, t)    δ = 3.78-3.90                  ppm          (6H, m)    δ = 4.18                  ppm          (2H, m)    δ = 5.10                  ppm          (1H, t)    δ = 7.17                  ppm          (2H, d,d)    δ = 8.22                  ppm          (2H, d,d)    ______________________________________

Catalytic hydrogenation of 360 g of the above nitro compound in 1,500 mlof methanol in the presence of Raney nickel at 65° C. and a hydrogenpressure of 70 bar gives a solution which, after filtering off thenickel and evaporating the filtrate towards the end in vacuo, leaves theamine of the formula ##STR578## as a brown oil.

¹ H-NMR (D₆ -DMSO)

    ______________________________________    δ = 3.26                  ppm          (2H, t)    δ = 3.41                  ppm          (2H, t)    δ = 3.70                  ppm          (2H, t)    δ = 3.82-3.88                  ppm          (4H, m)    δ = 3.95                  ppm          (2H, m)    δ = 5.07                  ppm          (1H, t)    δ = 6.50                  ppm          (2H, d,d)    δ = 6.66                  ppm          (2H, d,d)    ______________________________________

Running 100 g of the above oil into 250 ml of 96% pure sulphuric acid at0°-3° C., stirring the mixture at 0° C. for a few hours, stirring itinto 1.8 kg of ice, liming the solution with 410 g of CaCO₃ up to a pHof 4.7, filtering off the calcium sulphate and concentrating thesolution in vacuo down to 500 ml gives a solution of the substance ofthe formula ##STR579## which is suitable for synthetic purposes andwhose content can be determined by titration with sodium nitrite.

If the above amino-β-hydroxyethylsulphonyl-alkoxybenzene is run into 20%strength oleum instead of 96% pure sulphuric acid, the mixture isstirred until it is completely sulphonated and sulphated at 20° C.,suitable workup gives the solution of a compound of the formula##STR580## which, determining its content, can also be used forsynthetic purposes.

EXAMPLE 181

80.0 g of the compound of the formula ##STR581## prepared by theprocedure given in European Patent 0,355,492 are stirred into 160 ml of96% pure sulphuric acid at 0° C. The mixture is allowed to reach 20° C.over a period of 1 hour, the solution is poured onto 800 g of ice and320 ml of water, the prism-like crystals, after additional stirring fora short period, are filtered off with suction and the adhering sulphuricacid is displaced by washing with isopropanol. The product can be driedat 50° C. in vacuo. It has the formula ##STR582##

If the above compound is stirred into 20% strength oleum instead of into96% pure sulphuric acid, and the product is then worked up, as describedin Example 180, by adding CaCO₃ to the aqueous sulphuric acid solution,the solution of a compound of the formula ##STR583## is obtained, which,after determining its content, can also be used for dyestuff syntheses.

EXAMPLE 182

3.0 g of pyridine-3-carboxylic acid are added, after coupling, to adyestuff solution synthesised according to Example 1. The solution isheated to 75° to 80° C. and the pH is maintained at 7.0 with 2N sodiumcarbonate solution until the exchange of a fluorine atom for thenicotinic acid radical is complete. After cooling, the dyestuff can besalted out or the solution, after desalting and concentrating, can beused as a liquid dyestuff.

The dyestuff has the formula ##STR584## and dyes cotton, similarly tothe dyestuff from Example 1, from a long liquor.

The other fluoro- or chlorotriazine dyestuffs described in the precedingexamples can also be converted into the 3-carboxypyridiniumtriazinedyestuffs in a similar manner.

EXAMPLE 183

The products obtained in Example 179 can also be prepared in thefollowing manner:

209 g of 2-nitrophenol, 262 g of 1,3-bromochloropropane and 228 g ofpotassium carbonate are heated to 60° C. in 1,000 ml of ethanol and thenrefluxed until the 2-nitrophenol has disappeared. The reaction productof the formula ##STR585## can be precipitated from the mixture obtainedby dilution with 5 l of water in the form of a yellow oil.

The intermediate can either be converted directly without isolating itor after dissolving it again in 1,000 ml of ethanol or acetonitrile tothe thioether ##STR586## using 156 g of 2-mercaptoethanol and 276 g ofpotassium carbonate at 60°-80° C. and this thioether can be oxidised inthe known manner after the dilution of the solution with 3 l of waterand addition of 4.5 g of sodium tungstate at 55°-60° C. and 35% strengthH₂ O₂. The nitrosulphone obtained of the formula ##STR587## is reduced,in the manner described in Example 179, catalytically to give the aminocompound, which can then be either sulphated or sulphated andsulphonated.

The corresponding m and p compounds can be prepared analogously from m-or p-nitrophenol and 1,3-bromochloropropane.

We claim:
 1. A reactive dyestuff of the formula ##STR588## in which Ddenotes a radical of an organic dyestuff,W denotes a direct bond orbridging member, R₁ denotes H or alkyl, R₂ denotes H or alkyl, R denotesH, C₁ -C₂ -alkyl, halogen, or C₁ -C₄ -alkoxy, B denotes ##STR589## Xdenotes F, Cl, ##STR590## Z denotes --CH═CH₂ --CH₂ --CH₂ --OSO₃ H, --CH₂--CH₂ --Cl, --CH₂ --CH₂ --Br, --CH₂ --CH₂ --S₂ O₃ H, --CH₂ --CH₂--O--CO--CH₃, --CH₂ --CH₂ --OPO₃ H₂, or --CH₂ --CH₂ --OH, n denotes 1 or2.
 2. A reactive dyestuff according to claim 1, characterised in that Dis a radical from the monoazo, polyazo, metal complex, anthraquinone,phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene,triphenylmethane, xanthene, thioxanthone or nitroaryl series.
 3. Areactive dyestuff according to claim 1 characterised in that W denotes:##STR591## in which R'₁ represents hydrogen or alkyl, and alkylenedenotes an alkylene radical having 1 to 6 C atoms.
 4. A reactivedyestuff according to claim 1, having one of the following formulas(VII)-(XXIII): ##STR592## where R₃ is alkyl, alkoxy, or halogen,R₄ is H,alkyl, aryl, hetaryl, or aralkyl R_(VII) is COOH, or CH₃ ##STR593##where R₃ is alkyl, alkoxy, or halogen, R₄ is alkyl, aralkyl, or aryl, R₅is alkyl, aryl, aralkyl, or hetaryl, R₆ is H, COOR₃, ##STR594## CN, CH₂--SO₃ H, SO₃ H, or ##STR595## ##STR596## where R₃ is alkyl, alkoxy, orhalogen, R₇ is H, alkyl, alkoxy, acylamino, amino, or ureido, o,p is ino or p position relative to the azo group ##STR597## where in (X) to(XIII): R₃ is alkyl, alkoxy, or halogen, R₇ is alkyl, alkoxy, oracylamino, R₈ is alkyl, alkoxy, acylamino, or ureido, o is in orthoposition relative to the azo group, R₉ is R₈, or NO₂, and for (XIII), Xis F, and ##STR598## where R₁₀ is H, C₁ -C₄ -alkyl, halogen, C₁ -C₄-alkoxy, carboxyl, or SO₃ H, R₁₁ is H, C₁ -C₄ -alkyl, or SO₃ H, R₁₂ isH, C₁ -C₄ -alkyl, Cl, or Br, R₁₃ is H, or C₁ -C₄ -alkyl, ##STR599##where R₄ is H, or alkyl, R₁₀ is H, SO₃ H, or COOH, Pc is Cu or Niphthalocyanine radical ##STR600## where R₈ is alkyl, halogen, oralkylsulphonyl, D is a substituent capable of complex formation,##STR601## where R₃ is alkyl, alkoxy, or halogen, K is the radical of acoupling component, ##STR602## where R₂ is alkyl, or halogen, R₃ isalkyl, or alkoxy, K is the radical of a coupling component ##STR603##where ##STR604## K is the radical of a coupling component R₃ is alkyl,alkoxy, or acylamino ##STR605## R₃ is alkyl, or alkoxy, R₈ is H, NH₂, oracylamino ##STR606## and wherein each of the formulas (XII) - (XXIII), Adenotes a radical of the formula: ##STR607##
 5. A process for the dyeingand printing of substrates using a reactive dyestuff by applying theretoa reactive dyestuff according to claim 8.